Manufacture of uf



Oct. 13, 1959 w.'s. cALco-TT MANUFACTURE oF my;

Filed April 13, 1945 2 Sheets-Sheet 1 Nm. NN

ms M/vlHuJvz Oct. 13, 1959 j w. s. cALco-nf 2,908,548

MANUFACTUBE oF UF.,

Filed April 13. 1945 ZSheets-Sheet 2 f2' /29' f3' f 24' i" if CS MANUFACTURE F UF4 William S.' Calcott, Woodstown, NJ., assignor to the United States of America as represented by the United States Atomic Energy Commission This invention relates to reactions involving gaseous hydrogen uoride as a reactant and particularly relates tot-he manufacture of uranium tetraiiuoride.

It is known that uranium tetraiiuoride may be prepared by the action of anhydrous hydrogen uoride upon uranium dioxide at elevated temperatures. The most advantageous temperatures for conducting the reaction lie` between 400 C. and 600 C., and for producing a product, free. from Vtraces of unreacted uranium dioxide temperatures of 500 Cfto 650 C. are desirable, at least toward the'end of the reaction period.

:g Ordinary materials of'construction suffer severely from Corrosion by hydrogen fluoride at these high temperatures. Iron and steel have a very short life. Metals such as nickel and copper disintegrate rapidly also. Moreover the-,disintegration of the apparatus during reaction results in substantial contamination of the uranium tetrauoride by metal iluorides of the metal used for constructing the apparatus. Thus, substantial quantities of nickel,` iron and copper may be found in the product.

It is an object of the present invention to convert uranium dioxide to uranium tetrafluoride in an environment conducive to the production of material substantially free from contaminating metallic impurities. It is a further object to provide an apparatus for carrying out the process which possesses a relatively long life com- Pared .to apparatuses previously employed for this purpose. Further objects will be apparent from the following general description and detailed illustrations of the invention.

i In'accordance vwith the invention, the material to be reacted with hydrogen fluoride is brought into intimate contact with anhydrous hydrogen iiuoride gas at reaction temperatures in an apparatus having the surfaces exposed tothe reactants composed of carbon.

`Preferably graphite or a substantially imprevious carbon such as the phenolic-resin-impregnated carbon known as Karbate is employed. The apparatus may be constructed in the form'of a reaction tube of such a materialor it may be built up from blocks or slabs of this material. Instead of employing carbon to provide the structural strength required for containing the reactants, it is possible to employ a reactor composed of a metal, such as steel, nickel, Monel, and Ythe like, coated with a carbon coating. Ordinary stove polish has been applied to such metallic containers to provide a satisfactory apparatus. An especially suitable coating material is the colloidal dispersion of graphite in IWater marketed as Aquadag VWhen apparatus constructed of metals is entirely coated with this material, a uranium tetrailuoride product can be obtained having a surprisingly low proportion of contaminating metallic impurities.

` .In the accompanying drawing Figure,` lrshows4 a form of apparatus comprising a .Karbate reaction tube, whichV has been used successfully in applying the present invention,

',Figure 2 is a longitudinal elevation showing a reactor built- :upfromJ graphite slabs or blocks,

"am o without carbon coatings to prevent contact of reactants` with the metal, and

Figure 6 is a sectional view showing schematically the apparatus of Figure 5 with protective canopies in place. With especial reference to `Figure 1, the numeral 1 designates a Karbate tubeabout 5 feet long and havingan inside diameter of -1% ,inches andan outside diameter of 2 inches. The tube 1 isjsupported within a steel jacket 2 having an inlet 3 and outlet 4 for passage of a temperature-controlling gas, e.g., nitrogen, through the jacket. This gas also serves as a diluent and carrier to remove any gases or vapors permeating the walls of the carbon tube. The jacket 2 is covered with heat insulation 5. Theends of the jacket are sealed by Stoppers 6 and 7 and the seals are wound with coppercooling coils.

8 and 9. The ends of the tube,l which extend beyond mannerlsuicient heat is generated the Stoppers 6 and 7, are wound with copper cooling coils 10 and 11 and are provided withielectrical connections 12 and 13 for applying an electrical current to the carbon tube. By using the carbon tube as a resistorV in this to provide the necesi sary reaction temperatures. I Y j With reference to Figures 2, 3, and 4 a metal plate 21 forms a base for the reactor box. The base 21 carries threeA pairs of arms '22', 22', 23, 23',` 24 and 2.4 welded to the edges of the base 21 in vertical positions so as to form a cage for the reactor. v if The reactor itself comprises oor member 25 which supports a pair of upright boards 26 and 26 forming theY side -walls Vfor the lower half of the reactor.f These boards,

' are cut away to provide ledges upon which a shelf 27 provides a better seal and a more satisfactory joint for the application of a carbon cement than obtainable by using a plain square edge. One end of the reactorV is `closed by end member 31' having inlet 32 and outlet 33 and the other end ofthe reactor is closed by a lower end member 34 and an upperl member 35. As shown in Figure 2. each of shelves 27 and 30 has one end ilush4 with the end member 31 and the other end stopping short of end members 34 and 35 respectively.v This construction provides a sinuous channel back and forth from the inlet 32 to the outleti33 so that gases passing from the inlet to the outlet make four passes the length of the reactor; As shown more clearly in Figure 4 the side walls and ends arel chamfered to provide a firm supportfor the end members'. All ofthe structural memberslZS to 35 are composed .of graphite'.

Metal clamps 36, 37, and 38 lit over the upper ends ,ofl arms 22 and 22', v23 and 23', and 24 and 24 so as to prevent separation of the Vends of the arms and consequent collapse of the assembly. VThe entire assembly is adapted for insertion in anfoven heated in any suitable V3 The apparatus, after assembly is complete, is placed in a heated oven and inlet 32 and outlet 33 are connected to the appropriate gas lines. After completion of the reaction` the assembly is removed yfrom the oven and progressively disassembled to recover'thereaction product from thefloor and shelves. ofthe reactor.-

With particular reference to Figures 5 and 6,v theY apparats illustrated in these-figures comprises a Monel reaction chamber 41 having gas inlet 42 and gas outlet 43. The reaction chamber contains a series of shelves 44, 45 and 46 adapted to support pans V47A for containing the material to be reacted. Shelves 44 and 46 are spaced from the end of the-reactor remote from the inlet and outlet and shelf 4S is spaced from the opposite end so as yto provide a sinuous gas passage through the reactor. The end of the reaction chamber remote from the gas connections is flanged to provide a mounting for the end piece 4,8 which is removably mounted bybolts 49 so thatthe pans 47 can be removed froml the apparatus. The end member 48 comprises a packed gland 50 forming a seal between this end of the reactor and shelf 45. The Monel metal is protected from furnace gases by a steel shell 51 which encases the reactor.

In order to protect the contents of pans 47 from metallic dust, canopies 52, 53, 54, and 55 may be provided for the three shelves and floor of the reactor. These canopies are open at the ends so as not to interfere with the ofw of gas through the apparatus. They are preferably constructed of Mone1 coated on both sides with a carbon paint such as Aquadag or stove polish. A copper gasket 56 is provided to prevent leakage of gas at the union of the end member 48 with the reactor body 41. In using this apparatus'it may be removably installed in the same manner as the apparatus of Figures 2, 3, and 4, or it may bepermanently installed in a suitably heated furnace providing access to the removable Vend piece 48. The charge is loaded and unloaded merely by inserting and withdrawing the pans.

The apparatus of Figure 5 may be used for the productionof a product low in metal content with or without the canopies shown in Figure 6. In general, it is suflicient to coat the inside of pans 47 with a carbon paint such as Aquadag or stove polish. However the canopies provide a ready means of` protecting the charge from contamination after the apparatus has become corroded to such an extent that there is a possibility of substantial contamination by metallic impurities dropping from the undersides of reactor` shelves into the pans directly beneath. Y

The following examples further illustrate the invention.

. Example 1 Into the center one-third of the carbon tube of theapparatus illustrated in, Figure l, 470 grams of uranium oxide was placed and uniformly distributed to provide a passage for reactionl gas above the solid material. The tube was heated to 500 C. by passing an alternating current of 9 to 10 amperes through the carbon. Hydrogen fluoride of 99% purity (containing less than 0.1% H2O) was passed into the tube at normal pressure atan average rate of 40 to 50 grams per hour until the gases contained less than 0.3% `Water as determined by a conductivity measurement. This operation required about 101/2 hours. During this period the temperature Was held between 500 and 540 C. A uranium tetrauoride product substantially free from metallic impurities and completely soluble in sulfuric acid was thus obtained.

Example 2 The process of Example 1 was repeated employing a reaction temperature of 425. to 450 C. and a time of 131/2 hours. They average current was 8.1 amperes. The. uranium tetrauoride productobtaned was substantially free-from metallic impurities but contained traces of insoluble'V materialindicating that the reaction was not quite. complete.

iL Example 3 Into an apparatus of the type illustrated in Figures 2, 3 and 4 300 pounds of uranium dioxide was charged, 75 pounds onto each of the four trays. The charge was distributed over the area of the trays by means of a rake so that each tray was coated uniformly except for about 2 inches at the outlet end, about l inch on each side and about 6 inches at the inlet end. After loading, the surface of the solid material was furrowed by means of a wooden mold so as to increase the surface area exposed to gases.

The graphite box was assembled; cracks were stopped by plugging with a carbon cement (Carbo-korez). The loaded reactor Was placed in the oven and the headers were connected for inlet and exhaust gases. The temperature was then raised by means of the furnace to about 500 C., all connections were tightened, and the temperature was raised further to about 560 C.l Nitrogen was passed through the box for live minutes while the temperature was maintained at about 560 C. Anhydrous hydrogen fluoride was then fed through the inlet header for one hour at approximately 1/2 pound pressure while the temperature was allowed to fall to about 540 C. After the rst hour the ow of anhydrous hydrogen fluoride was increased to about 13 pounds per hour while the temperature was maintained at 500 C. to 530 C. After 10 to 15 hours, the temperature was raised to about 575 C. the ilow of anhydrous hydrogen uoride was stopped, and hydrogen was passed through the box for 1/2 hour at a rate of 100 Ycu. ft. per hour, measured at standard temperature and pressure.

Ihe hydrogen flow was then stopped and anhydrous hydrogen iluoride ilow was resumed at a ow rate of about 13 pounds per hour for an additional 8 hours. The ilow of hydrogen fluoride was then stopped and nitrogen was passed through the reactor for about 10 minutes to expel unreacted hydrogen iluoride and water vapor. The reactor was then allowed to cool to room temperature. Cooling was expedited by removing the unit from the furnace and allowing it to cool in a gas-cooled chamber. The reactor was then opened and the charge of reaction product was removed by raking and scooping it from the carbon trays. A product containing less than 0.002% iron, less than 0.0004% nickel, and less than 0.000l% copper was readily obtainable in this manner.

Example 4 A Monel apparatus of the type illustrated in Figures 5 and 6 of the drawing was coated with Aquadag by applying the colloidal suspension with a paint brush and drying at C. The shelves were coated both on the top and bottom and pans 47 were coated on the inside. The pans were then charged with uranium dioxide and the oxide was converted to the tetrailuoride inthe manner described in Example 3. The product was found to contain 5 parts of nickel per million and 6 parts Vof copper per million. In other similar tests products containing from 0 to 12 parts of nickel and from less than one up to 6 parts of copper per million parts of solids were obtained.

Using canopies 52, 53, etc. coated with Aquadag and pans 47 similarly coated, a product having a purity within this same range was obtained.

Employing ordinary stove polish in place of Aquadag, products averaging about 1.3 parts of nickel and less than one part of copper per million parts of solid were obtained.

When the same apparatus was employed without coating the pans but using otherwise similar reaction conditions, the products averaged 'about 36 parts of nickel and 20 parts of copper per million parts of solids.

It will be understood that I intend to include variations and modifications of the invention and that the preceding examples are illustrations only and in no Wise to beconstrued as limitations upon thel invention, the score of which is dened in the appended claim, wherein I claim: A process of making very pure UF4 from U02 which comprises placing U02 in a reactor the inner surfaces of which consist of free unimpregnated carbon, raising and maintaining the temperature of the reactor in the range from 500 C. to 600 C., passing nitrogen through the reactor to flush out the air, then passing anyhdrous H F through the reactor in contact with the U02 for several hours, stopping the flow of HF and passing hydrogen through the reactor for less than an hour, then resuming the flow of HF through the reactor for several hours, stopping the ow of HF and passing nitrogen through the reactor for a few minutes to expel unreacted HF and Water vapor, cooling the reactor to room temperature and removing the UF4 that has been made therein.

References Cited in the le of this patent UNITED STATES PATENTS OTHER REFERENCES Friend: Textbook of Inorganic Chemistry, vol. 7, Pt. 3, page 291 (1926). Publ. by Charles Grin & Co., Ltd., London.

Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. l2, 1932, pages 73, 74.

Chem. Ind., May 1944, Recent Developments in Car- 20 bon Chemical Equipment, pp. 683-4, by Ollinger. 

